CN102604347B - Preparation method of chitosan modified polylactic acid material by gamma-ray irradiation - Google Patents
Preparation method of chitosan modified polylactic acid material by gamma-ray irradiation Download PDFInfo
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- CN102604347B CN102604347B CN201210048072.4A CN201210048072A CN102604347B CN 102604347 B CN102604347 B CN 102604347B CN 201210048072 A CN201210048072 A CN 201210048072A CN 102604347 B CN102604347 B CN 102604347B
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 32
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 32
- 230000005251 gamma ray Effects 0.000 title claims abstract description 29
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000007731 hot pressing Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- -1 poly(lactic acid) Polymers 0.000 claims description 44
- 229920002101 Chitin Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 230000005855 radiation Effects 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- 238000012986 modification Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 7
- 238000007789 sealing Methods 0.000 abstract description 2
- 230000009477 glass transition Effects 0.000 abstract 1
- 229920005615 natural polymer Polymers 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 230000007704 transition Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000930 thermomechanical effect Effects 0.000 description 5
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Materials For Medical Uses (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a preparation method of a chitosan modified polylactic acid material by gamma-ray irradiation. The preparation method comprises the steps of performing melt blending on polylactic acid, a natural polymer material of chitosan and a sensitizer, wherein the mass ratio of chitosan to polylactic acid is 0.5:100-20:100 and the mass ratio of the sensitizer to polylactic acid is 0.5:100-10:100; then performing hot pressing, cooling and demoulding forming; putting the obtained material into an irradiation bag and sealing after vacuumizing or introducing nitrogen; and performing irradiation treatment by Co-60 gamma-ray at room temperature to obtain the chitosan modified polylactic acid material. The chitosan modified polylactic acid material prepared by the preparation method is good in thermodynamic property, the gel fraction is 60-85%, the glass transition temperature is 64-70 DEG C and the tensile strength is 68-79MPa, and the properties are remarkably improved in comparison with those before modification, so that the chitosan modified polylactic acid material is wide in application prospect.
Description
Technical field
The present invention relates to a kind of gamma-ray irradiation preparation method of chitin modified poly-lactic acid material.
Background technology
Poly(lactic acid) is to prepare with the plant resources such as corn, stalk, abundant raw material, and there is the advantages such as nontoxic, fully biodegradable, environmental protection, be a kind of environmentally friendly novel material, be subject to gradually people's high praise, there is very wide application space and development prospect.But poly(lactic acid) is those semi-crystalline materials, its second-order transition temperature (Tg) is 60 DEG C of left and right, and this has greatly limited it and has applied.Poly(lactic acid) is by the lactic acid molecules polycondensation that contains hydroxyl and carboxyl, contain a large amount of unreacted hydroxyls and carboxylic group in high molecular end, it has certain activity, in lasting complicated environment for use, can a series of variations occur and the stability of product and work-ing life are greatly affected.
There are a large amount of researchers to be devoted to the study on the modification work of poly(lactic acid) both at home and abroad, are intended to make up himself defect, improve its thermomechanical property and stability, further expand its application space.Filling and blending method are one of polylactic acid modified methods of commonly using, it has the advantages such as reaction system is simple, easy and simple to handle, but the consistency of poly(lactic acid) and most plasticising and packing material, polarity and crystallinity there are differences, low interface bond strength and the thermomechanical property causing that is separated decline and the uncontrollable subject matter that becomes of degradation property.Research shows, can effectively promote the thermomechanical property of poly(lactic acid) by the method for chemically crosslinked and branching, but generally need and build more complicated reaction system by initiator, has affected to a certain extent poly-lactic acid material environmental protection and biodegradation character.
Gamma-rays has very high energy, can act on material and causes atom or molecule ionization occurs and excite, and can change rapidly free radical and neutral molecule into and cause complicated chemical transformation, to realize modification to material or the preparation of novel material.Compared with traditional method of modifying, gamma-ray irradiation method has lot of superiority, as modifying process carries out at normal temperatures, is simply easy to promote; Reaction system is pure, avoids introducing too much reactant, does not need initiator, environmental protection; Ray penetration power is strong, and reaction conditions is even etc.In recent years, gamma-ray irradiation method has been widely used in modification and the preparation of material as a kind of effective synthesizing mean.
Summary of the invention
The technical problem solving: the object of the invention is to adopt strengthening radiation crosslinking to make up the deficiency of existing poly-lactic acid material modification technology, propose a kind of method that adopts gamma-ray irradiation technology to prepare chitin modified poly-lactic acid material, the method is easy and simple to handle, be easy to promote.The poly-lactic acid material that this method modification obtains has kept environmental protection and biodegradable characteristic, has again good thermomechanical property, has wide application space.
Technical scheme: a kind of gamma-ray irradiation preparation method of chitin modified poly-lactic acid material, by poly(lactic acid), natural macromolecular material chitosan and sensitizing agent melt blending, wherein the mass ratio of chitosan and poly(lactic acid) is 0.5: 100～20: 100, the mass ratio of sensitizing agent and poly(lactic acid) is 0.5: 100～10: 100, Hot-press cooling stripping forming, resulting materials is put into irradiation bag vacuumizes or inflated with nitrogen after seal, under room temperature condition, utilize Co-60 gamma-rays to carry out radiation treatment to it, obtain chitin modified poly-lactic acid material.
Described natural macromolecular material chitosan molecule amount is 10
3～10
5.
Described sensitizing agent is triallyl isocyanurate, Viscoat 295, the acid of pentaerythritol triacrylate or two (TriMethylolPropane(TMP)) tetrapropylene.
Described poly(lactic acid), chitosan and sensitizing agent blending temperature are 150～240 DEG C, and the blend time is 10min～2h, and hot-forming temperature is 100～180 DEG C, hot pressing time 20min～1h, and pressure is 5～15MPa, naturally cooling stripping forming.
Described Co-60 gamma-ray irradiation condition is radiation dose rate 0.5～10KGyh
-1, absorption dose 5～150KGy.
In the method for the invention, the structural formula of sensitizing agent is as follows:
Triallyl isocyanurate Viscoat 295
Two (TriMethylolPropane(TMP)) tetrapropylene acid pentaerythritol triacrylate
Beneficial effect: the present invention adopts gamma-ray irradiation technology modified polylactic acid material, this technology has the not available advantages of conventional chemical modification approach such as reaction system pure (not needing to add initiator), high efficient and reliable, environmental protection, simple to operate, be easy to promote; Natural macromolecular material chitosan is added modified system by the present invention, greatly reduced the consumption of traditional linking agent, not only effectively improved the performance of poly-lactic acid material but also keep its environmental protection and biodegradation character; Adopt the prepared chitin modified poly-lactic acid material of present method to there is good thermomechanical property, gel fraction 60%～85%, 64 DEG C～70 DEG C of second-order transition temperatures, tensile strength 68MPa～79MPa, its obvious raising compared with performance before modification, has broad application prospects.
Embodiment
Below by the mode of embodiment, technical solution of the present invention is elaborated, but protection scope of the present invention is not limited to described embodiment.
Embodiment 1:
First poly(lactic acid) is put into 60 DEG C of dry 2h of vacuum drying oven, taken 100g poly(lactic acid) and add successively chitosan (molecular weight approximately 4000) 1.5g, triallyl isocyanurate 1.5g, mixed at room temperature; Said mixture is heated to 190 DEG C, stirs 1h, mix; The melts mixing is poured in the mould of preheating (90 DEG C-120 DEG C), on vulcanizing press, gradation is forced into 10MPa, and 150 DEG C of hot pressing 30min keep above-mentioned pressure cooling forming, the demoulding; The material obtaining is put into after irradiation bag is full of nitrogen and sealed, put into Co-60 gamma-ray irradiation center and carry out radiation treatment under room temperature condition, gamma-ray irradiation dose rate is about 2KGyh
-1, in the time that absorption dose reaches 50KGy, irradiation bag is taken out, obtain chitin modified poly-lactic acid material.
Sample test result shows, after gamma-ray irradiation, the gel fraction of chitin modified poly-lactic acid material is 83%, second-order transition temperature is that 70 DEG C, tensile strength reach 78MPa.
Embodiment 2:
First poly(lactic acid) is put into 60 DEG C of dry 2h of vacuum drying oven, taken 100g poly(lactic acid) and add successively chitosan (molecular weight approximately 4000) 2.5g, triallyl isocyanurate 2.5g, mixed at room temperature; Said mixture is heated to 190 DEG C, stirs 1h, mix; The melts mixing is poured in the mould of preheating (90 DEG C-120 DEG C), on vulcanizing press, gradation is forced into 10MPa, and 150 DEG C of hot pressing 30min keep above-mentioned pressure cooling forming, the demoulding; The material obtaining is put into after irradiation bag is full of nitrogen and sealed, put into Co-60 gamma-ray irradiation center and carry out radiation treatment under room temperature condition, gamma-ray irradiation dose rate is about 2KGyh
-1, in the time that absorption dose reaches 40KGy, irradiation bag is taken out, obtain chitin modified poly-lactic acid material.
Sample test result shows, after gamma-ray irradiation, the gel fraction of chitin modified poly-lactic acid material is 80%, second-order transition temperature is that 68 DEG C, tensile strength are 77MPa.
Embodiment 3
First poly(lactic acid) is put into 60 DEG C of dry 2h of vacuum drying oven, taken 100g poly(lactic acid) and add successively chitosan (molecular weight is 10
3～10
5) 0.5g, Viscoat 295 0.5g, mixed at room temperature; Said mixture is heated to 240 DEG C, stirs 2h, mix; The melts mixing is poured in the mould of preheating (90 DEG C-120 DEG C), on vulcanizing press, gradation is forced into 10MPa, and 180 DEG C of hot pressing 1h keep above-mentioned pressure cooling forming, the demoulding; After the material obtaining is put into the sealing of irradiation bag, vacuumize (vacuum tightness-0.09MPa), put into Co-60 gamma-ray irradiation center and carry out radiation treatment under room temperature condition, gamma-ray irradiation dose rate is about 10KGyh
-1, in the time that absorption dose reaches 150KGy, irradiation bag is taken out, obtain chitin modified poly-lactic acid material.
Sample test result shows, after gamma-ray irradiation, the gel fraction of chitin modified poly-lactic acid material is 78%, second-order transition temperature is that 66 DEG C, tensile strength are 73MPa.
Embodiment 4
First poly(lactic acid) is put into 60 DEG C of dry 2h of vacuum drying oven, taken 100g poly(lactic acid) and add successively chitosan (molecular weight is 10
3～10
5) 20g, pentaerythritol triacrylate 10g, mixed at room temperature; Said mixture is heated to 180 DEG C, stirs 1h, mix; The melts mixing is poured in the mould of preheating (90 DEG C-120 DEG C), on vulcanizing press, gradation is forced into 10MPa, and 150 DEG C of hot pressing 0.5h keep above-mentioned pressure cooling forming, the demoulding; The material obtaining is put into after irradiation bag is full of nitrogen and sealed, put into Co-60 gamma-ray irradiation center and carry out radiation treatment under room temperature condition, gamma-ray irradiation dose rate is about 5KGyh
-1, in the time that absorption dose reaches 100KGy, irradiation bag is taken out, obtain chitin modified poly-lactic acid material.
Sample test result shows, after gamma-ray irradiation, the gel fraction of chitin modified poly-lactic acid material is 76%, second-order transition temperature is that 67 DEG C, tensile strength are 71MPa.
Embodiment 5
First poly(lactic acid) is put into 60 DEG C of dry 2h of vacuum drying oven, taken 100g poly(lactic acid) and add successively chitosan (molecular weight is 10
3～10
5) 10g, two (TriMethylolPropane(TMP)) tetrapropylene acid 5g, mixed at room temperature; Said mixture is heated to 180 DEG C, stirs 1h, mix; The melts mixing is poured in the mould of preheating (90 DEG C-120 DEG C), on vulcanizing press, gradation is forced into 10MPa, and 150 DEG C of hot pressing 0.6h keep above-mentioned pressure cooling forming, the demoulding; The material obtaining is put into after irradiation bag is full of nitrogen and sealed, put into Co-60 gamma-ray irradiation center and carry out radiation treatment under room temperature condition, gamma-ray irradiation dose rate is about 4KGyh
-1, in the time that absorption dose reaches 100KGy, irradiation bag is taken out, obtain chitin modified poly-lactic acid material.Sample test result shows, after gamma-ray irradiation, the gel fraction of chitin modified poly-lactic acid material is 75%, second-order transition temperature is that 65 DEG C, tensile strength are 69MPa.
Claims (1)
1. the gamma-ray irradiation preparation method of a chitin modified poly-lactic acid material, it is characterized in that first poly(lactic acid) being put into 60 DEG C of dry 2h of vacuum drying oven, take chitosan 1.5g, triallyl isocyanurate 1.5g that 100g poly(lactic acid) also adds molecular weight 4000 successively, mixed at room temperature; Said mixture is heated to 190 DEG C, stirs 1 h, mix; The melts mixing is poured in the mould of 90 DEG C-120 DEG C of preheatings, on vulcanizing press, gradation is forced into 10 MPa, and 150 DEG C of hot pressing 30 min, keep above-mentioned pressure cooling forming, the demoulding; The material obtaining is put into after irradiation bag is full of nitrogen and sealed, put into Co-60 gamma-ray irradiation center and carry out radiation treatment under room temperature condition, gamma-ray irradiation dose rate is 2 KGyh
-1, in the time that absorption dose reaches 50 KGy, irradiation bag is taken out, obtain chitin modified poly-lactic acid material.
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| CN105732843B (en) * | 2016-03-07 | 2018-01-12 | 浙江省能源与核技术应用研究院 | A kind of method of electron beam irradiation and ray sensitizer interaction degraded macromolecular amount chitosan |
| CN106064076B (en) * | 2016-06-08 | 2018-11-09 | 南京航空航天大学 | A kind of method that irradiation prepares alginic acid modification load carbon zeolite |
| CN107419434B (en) * | 2017-08-16 | 2019-02-19 | 江门华大生物科技有限公司 | A kind of preparation method of preservative free non-woven fabrics facial mask |
| CN108286132B (en) * | 2018-03-27 | 2020-06-23 | 界首市圣通无纺布有限公司 | Processing method of easily-degradable non-woven fabric with antibacterial function |
| CN109134892B (en) * | 2018-10-22 | 2019-05-14 | 广州华大生物科技有限公司 | A kind of gamma-ray irradiation preparation method of chitin modified poly-lactic acid material |
| CN109536159B (en) * | 2018-12-14 | 2019-10-22 | 南京航空航天大学 | A method of quantum dot fluorescence performance is improved using radiation |
| CN116333468B (en) * | 2022-12-23 | 2024-05-31 | 中广核俊尔(浙江)新材料有限公司 | Heat-shrinkage-resistant high-flow polylactic acid material |
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| CN101225221B (en) * | 2007-12-27 | 2011-05-11 | 四川大学 | Polylactic acid and electron beam radiation modifying method for copolymer composite material thereof |
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